The present invention relates to an electron donor of an olefin polymerization catalyst, a novel phthalic acid diester derivative used as a plasticizer for resins such as vinyl chloride, a component for intermediates for the preparation of various compounds, and an electron donor used in the olefin polymerization catalyst containing the phthalic acid diester derivative.
Conventionally, phthalic acid diesters have been used as a common plasticizer for vinyl chloride. Diethyl phthalate, dibutyl phthalate, and di-iso-octyl phthalate are typical phthalic acid diesters. In the technology for polymerizing olefins, typically propylene, in the presence of a solid catalyst comprising magnesium and titanium as major components, an electron donor (an internal electron donor) is added to the solid catalyst to improve the stereoregularity of the formed polymer and the polymerization activity. A number of reports have proposed the use of specific phthalic acid esters as such an electron donor.
As a prior art using a phthalic acid diester as one of the components of the olefin polymerization catalyst, Japanese Unexamined Patent Publication No. (hereinafter referred to as JP-A) 63310/1982 and JP-A No. 63311/1982, for example, disclose a method of polymerizing olefins having three or more carbon atoms using a combined catalyst comprising a solid catalyst component containing a magnesium compound, titanium compound, and an electron donor such as a diester compound, e.g., phthalic acid ester, an organoaluminum compound, and an organosilicon compound having a Sixe2x80x94Oxe2x80x94C linkage. JP-A 6006/1989 discloses a solid catalyst component for olefin polymerization containing an alkoxymagnesium, titanium tetrachloride, and dibutyl phthalate. The solid catalyst component was proven to be successful to some extent in producing a stereoregular propylene polymer at a high yield.
The polymers produced using these catalysts are used in a variety of applications including formed products such as parts of vehicles and household electric appliances, containers, and films. These products are manufactured by melting polymer powders produced by the polymerization and by forming the melted polymer using any one of various molds. In manufacturing formed products, particularly large products, by injection molding, melted polymers are sometimes required to have high fluidity (melt flow rate). Accordingly, a number of studies have been undertaken to increase the melt flow rate of polymers.
The melt flow rate greatly depends on the molecular weight of the polymers. In the polymer industry, hydrogen is generally used as a molecular weight regulator for polymers in the polymerization of olefins. In this instance, a large quantity of hydrogen is usually added to produce low molecular weight polymers which are the polymers having a high melt flow rate. However, the quantity of hydrogen which can be added is limited because of the pressure resistance of the reactor from the viewpoint of safety. In order to add a larger amount of hydrogen, the partial pressure of monomers to be polymerized has to be decreased. The decrease in the partial pressure, however, is accompanied by a decrease in the productivity. Additionally, use of a large amount of hydrogen may bring about a problem of cost. Development of a catalyst capable of producing polymers with a high melt flow rate by using a smaller amount of hydrogen, in other words, a catalyst which has a high activity to hydrogen or high response to hydrogen and which produces a highly stereoregular polymer at a high yield has therefore been desired. In the above-mentioned prior art, however, it is not sufficient to solve such a problem.
Accordingly, an object of the present invention is to provide a novel phthalic acid diester derivative useful as one of the components for an olefin polymerization catalyst, particularly a catalyst for the polymerization of propylene or ethylene, having a high response to hydrogen, which can produce polymers having high stereoregularity in an extremely high activity and high yield, and an electron donor used as an olefin polymerization catalyst containing the phthalic acid diester derivative as an effective component.
The present inventors have conducted extensive studies to solve the problems in conventional technologies relating to the catalysts for the polymerization of olefins. As a result, the present inventors have discovered a novel phthalic acid diester derivative which is extremely effective as an electron donor used as one of the components of such a catalyst. Confirmation of such an effect has led to the completion of the present invention.
Specifically, the above object is achieved in the present invention by a phthalic acid diester derivative of the following formula (1), 
wherein R1 is an alkyl group having 1 to 8 carbon atoms or a halogen atom; R2 and R3 may be either identical or different, representing an alkyl group having 1 to 12 carbon atoms; and n, which indicates the number of R1, is 1 or 2, provided that when n is 2, the two R1 groups may be either identical or different.
The above object is further achieved in the present invention by an electron donor used in a catalyst for the polymerization of olefins comprising a phthalic acid diester derivative of the above formula (1) as an effective component.
In the phthalic acid diester derivative of the present invention, given as examples of the alkyl group having 1 to 8 carbon atoms represented by R1 of the formula (1) are a methyl group, an ethyl group, a n-propyl group, an iso-propyl group, a n-butyl group, an iso-butyl group, a t-butyl group, a n-pentyl group, an iso-pentyl group, a neopentyl group, a n-hexyl group, an iso-hexyl group, a 2,2-dimethylbutyl group, a 2,2-dimethyl pentyl group, a iso-octyl group, and a 2,2-dimethylhexyl group. As halogen atoms represented by R1, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be given. Of these groups represented by R1, preferable groups are a methyl group, an ethyl group, a t-butyl group, a chlorine atom, a fluorine atom, and a bromine atom, with the methyl group, t-butyl group, chlorine atom, fluorine atom, and bromine atom being particularly preferable.
The groups represented by R2 or R3 include a methyl group, an ethyl group, a n-propyl group, an iso-propyl group, a n-butyl group, an iso-butyl group, a t-butyl group, a n-pentyl group, an iso-pentyl group, a neopentyl group, a n-hexyl group, an iso-hexyl group, a 2,2-dimethylbutyl group, a 2,2-dimethyl pentyl group, an iso-octyl group, a 2,2-dimethylhexyl group, a n-nonyl group, an iso-nonyl group, a n-decyl group, an iso-decyl group, and a n-dodecyl group. Of these, an ethyl group, a n-butyl group, an iso-butyl group, a t-butyl group, a neopentyl group, an iso-hexyl group, and an iso-octyl group are preferable, with an ethyl group, a n-butyl group, a neopentyl group, and an iso-hexyl group being particularly preferable.
The symbol n, which indicates the number of R1, is 1 or 2, provided that when n is 2, the two R1 groups may be either identical or different. When n=1, the substituent R1 replaces the hydrogen atom at the 3, 4, or 5 position of the phthalic acid diester derivative, and when n=2, R1 replaces the hydrogen atoms at the 4 and 5 positions.
Preferable phthalic acid diester derivatives are compounds having the structure of the formula (1), wherein n=1 or 2, R1 is an alkyl group with 1 to 5 carbon atoms or a halogen atom, and R2 and R3 are alkyl groups with 4 to 8 carbon atoms including a tertiary carbon atom.
Specific examples of the compounds of the above formula (1), wherein n=1 or 2, R1 is an alkyl group with 1 to 5 carbon atoms or a halogen atom, and R2 and R3 are alkyl groups with 4 to 8 carbon atoms including a tertiary carbon atom, include dineopentyl 3-methylphthalate, dineopentyl 4-methylphthalate, dineopentyl 3-ethylphthalate, dineopentyl 4-ethylphthalate, t-butylneopentyl 3-methylphthalate, t-butylneopentyl 4-methylphthalate, t-butyl neopentyl 3-ethylphthalate, t-butylneopentyl 4-ethylphthalate, dineopentyl 4,5-dimethyl phthalate, dineopentyl 4,5-diethyl phthalate, t-butyl dineopentyl 4,5-dimethylphthalate, t-butyl neopentyl 4,5-diethylphthalate,dineopentyl 3-fluorophthalate, dineopentyl 3-chlorophthalate, dineopentyl 4-chlorophthalate, dineopentyl 4-bromophthalate, and dineopentyl 4-t-butyl phthalate. Of these compounds dineopentyl 4-methylphthalate, dineopentyl 4,5-dimethylphthalate, dineopentyl 4-ethyl phthalate, dineopentyl 4,5-diethylphthalate, dineopentyl 4-bromophthalate, dineopentyl 3-fluorophthalate, and dineopentyl 4-t-butylphthalate are particularly preferable.
Specific examples of the compounds of the above formula (1), wherein n=2, one of the groups R1 is a halogen atom and the other is an alkyl group with 1 to 8 carbon atoms, and at least one of the groups R2 and R3 is an alkyl group with 1 to 12 carbon atoms other than the alkyl group with 4 to 8 carbon atoms including a tertiary carbon atom include: diethyl 4-methyl-5-chlorophthalate, diethyl 4-methyl-5-bromo phthalate, diethyl 4-ethyl-5-chlorophthalate, diethyl 4-ethyl-5-bromophthalate, di-n-butyl 4-methyl-5-chlorophthalate, di-n-butyl 4-methyl-5-bromophthalate, di-n-butyl 4-ethyl-5-chlorophthalate, di-n-butyl 4-ethyl-5-bromophthalate, diisobutyl 4-methyl-5-chlorophthalate, diisobutyl 4-methyl-5-bromophthalate, diisobutyl 4-ethyl-5-chloro phthalate, diisobutyl 4-ethyl-5-bromophthalate, diisohexyl 4-methyl-5-chlorophthalate, diisohexyl 4-methyl-5-bromo phthalate, diisohexyl 4-ethyl-5-chlorophthalate, diisohexyl 4-ethyl-5-bromophthalate, diisooctyl 4-methyl-5-chloro phthalate, diisooctyl 4-methyl-5-bromophthalate, diisooctyl 4-ethyl-5-chlorophthalate, diisooctyl 4-ethyl-5-bromo phthalate, ethyl-n-butyl 4-methyl-5-chlorophthalate, ethyl-n-butyl 4-chloro-5-methyl phthalate, ethyl-n-butyl 4-methyl-5-bromophthalate, ethyl-n-butyl 4-bromo-5-methyl phthalate, ethyl-n-butyl 4-ethyl-5-chlorophthalate, ethyl-n-butyl 4-chloro-5-ethylphthalate, ethyl-n-butyl 4-ethyl-5-bromo phthalate, ethyl-n-butyl 4-bromo-5-ethylphthalate, ethyl isobutyl 4-methyl-5-chlorophthalate, ethylisobutyl 4-chloro-5-methylphthalate, ethylisobutyl 4-methyl-5-bromo phthalate, ethylisobutyl 4-bromo-5-methylphthalate, ethyl isobutyl 4-ethyl-5-chlorophthalate, ethyl isobutyl 4-chloro-5-ethylphthalate, ethylisobutyl 4-ethyl-5-bromophthalate, ethylisobutyl 4-bromo-5-ethylphthalate, ethylisohexyl 4-methyl-5-chlorophthalate, ethylisohexyl 4-chloro-5-methylphthalate, ethylisohexyl 4-methyl-5-bromophthalate, ethylisohexyl 4-bromo-5-methylphthalate, ethylisohexyl 4-ethyl-5-chlorophthalate, ethylisohexyl 4-chloro-5-ethyl phthalate, ethylisohexyl 4-ethyl-5-bromophthalate, ethyl isohexyl 4-bromo-5-ethylphthalate, n-butylisobutyl 4-methyl-5-chlorophthalate, n-butylisobutyl 4-chloro-5-methyl phthalate, n-butylisobutyl 4-methyl-5-bromophthalate, n-butylisobutyl 4-bromo-5-methyl phthalate, n-butylisobutyl 4-ethyl-5-chlorophthalate, n-butyl isobutyl 4-chloro-5-ethylphthalate, n-butylisobutyl 4-ethyl-5-bromophthalate, n-butylisobutyl 4-bromo-5-ethylphthalate, n-butylisohexyl 4-methyl-5-chlorophthalate, n-butylisohexyl 4-chloro-5-methylphthalate, n-butylisohexyl 4-methyl-5-bromo phthalate, n-butylisohexyl 4-bromo-5-methylphthalate, n-butyl isohexyl 4-ethyl-5-chlorophthalate, n-butylisohexyl 4-chloro-5-ethylphthalate, n-butylisohexyl 4-ethyl-5-bromophthalate, and n-butylisohexyl 4-bromo-5-ethylphthalate.
Specific examples of the compounds of the above formula (1), wherein n=1 or 2, R1 is an alkyl group with 1 to 8 carbon atoms, and R2 and R3 are alkyl groups with 1 to 12 carbon atoms other than the alkyl group with 4 to 8 carbon atoms including a tertiary carbon atom include diethyl 3-methylphthalate, diethyl 4-methylphthalate, diethyl 3-ethylphthalate, diethyl 4-ethylphthalate, diethyl 3-t-butylphthalate, diethyl 4-t-butyl phthalate, diethyl 3-n-butylphthalate, diethyl 4-n-butylphthalate, diethyl 4,5-dimethylphthalate, diethyl 4,5-diethylphthalate, diethyl 4-methyl-5-ethylphthalate, diethyl 4-methyl-5-t-butylphthalate, diethyl 4-ethyl-5-t-butylphthalate, di-n-butyl 3-methylphthalate, di-n-butyl 4-methylphthalate, di-n-butyl 3-ethylphthalate, di-n-butyl 4-ethylphthalate, di-n-butyl 3-t-butylphthalate, di-n-butyl 4-t-butylphthalate, di-n-butyl 3-n-butylphthalate, di-n-butyl 4-n-butylphthalate, di-n-butyl 4,5-dimethylphthalate, di-n-butyl 4,5-diethylphthalate, di-n-butyl 4-methyl-5-ethyl phthalate, di-n-butyl 4-methyl-5-t-butylphthalate, di-n-butyl 4-ethyl-5-t-butylphthalate, diisobutyl 3-methyl phthalate, diisobutyl 4-methylphthalate, diisobutyl 3-ethyl phthalate, diisobutyl 4-ethylphthalate, diisobutyl 3-t-butyl phthalate, diisobutyl 4-t-butylphthalate, diisobutyl 3-n-butylphthalate, diisobutyl 4-n-butylphthalate, diisobutyl 4,5-dimethylphthalate,-diisobutyl 4,5-diethylphthalate, diisobutyl 4-methyl-5-ethylphthalate, diisobutyl 4-methyl-5-t-butylphthalate, diisobutyl 4-ethyl-5-t-butylphthalate, diisohexyl 3-methylphthalate, diisohexyl 4-methylphthalate, diisohexyl 3-ethylphthalate, diisohexyl 4-ethylphthalate, diisohexyl 3-t-butylphthalate, diisohexyl 4-t-butylphthalate, diisohexyl 3-n-butylphthalate, diisohexyl 4-n-butylphthalate, diisohexyl 4,5-dimethylphthalate, diisohexyl 4,5-diethyl phthalate, diisohexyl 4-methyl-5-ethylphthalate, diisohexyl 4-methyl-5-t-butylphthalate, diisohexyl 4-ethyl-5-t-butyl phthalate, diisooctyl 3-methylphthalate, diisooctyl 4-methyl phthalate, diisooctyl 3-ethylphthalate, diisooctyl 4-ethyl phthalate, diisooctyl 3-t-butylphthalate, diisooctyl 4-t-butylphthalate, diisooctyl 3-n-butylphthalate, diisooctyl 4-n-butylphthalate, diisooctyl 4,5-dimethylphthalate, diisooctyl 4,5-diethylphthalate, diisooctyl 4-methyl-5-ethyl phthalate, diisooctyl 4-methyl-5-t-butylphthalate, diisooctyl 4-ethyl-5-t-butylphthalate, di-n-decyl 4-methyl phthalate, diisodecyl 4-methylphthalate, di-n-decyl 4-ethyl phthalate, diisodecyl 4-ethylphthalate, ethyl-n-butyl 3-methylphthalate, ethyl-n-butyl 4-methylphthalate, ethyl-n-butyl 3-ethylphthalate, ethyl-n-butyl 4-ethylphthalate, ethyl-n-butyl 3-t-butylphthalate, ethyl-n-butyl 4-t-butyl phthalate, ethyl-n-butyl 4,5-dimethylphthalate, ethyl-n-butyl 4,5-diethylphthalate, ethyl-n-butyl 4-methyl-5-ethylphthalate, ethyl-n-butyl 4-ethyl-5-methylphthalate, ethylisobutyl 3-methylphthalate, ethylisobutyl 4-methyl phthalate, ethylisobutyl 3-ethylphthalate, ethylisobutyl 4-ethyl phthalate, ethylisobutyl 3-t-butylphthalate, ethyl isobutyl 4-t-butylphthalate, ethylisobutyl 4,5-dimethyl phthalate, ethyl isobutyl 4,5-diethylphthalate, ethyl isobutyl 4-methyl-5-ethylphthalate, ethylisobutyl 4-ethyl-5-methylphthalate, ethylisohexyl 3-methylphthalate, ethyl isohexyl 4-methylphthalate, ethylisohexyl 3-ethylphthalate, ethylisohexyl 4-ethylphthalate, ethylisohexyl 3-t-butyl phthalate, ethylisohexyl 4-t-butylphthalate, ethylisohexyl 4,5-dimethylphthalate, ethylisohexyl 4,5-diethylphthalate, ethylisohexyl 4-methyl-5-ethylphthalate, ethylisohexyl 4-ethyl-5-methylphthalate, n-butylisobutyl 3-methyl phthalate, n-butylisobutyl 4-methylphthalate, n-butyl isobutyl 3-ethylphthalate, n-butylisobutyl 4-ethylphthalate, n-butylisobutyl 3-t-butylphthalate, n-butylisobutyl 4-t-butylphthalate, n-butylisobutyl 4,5-dimethylphthalate, n-butylisobutyl 4,5-diethylphthalate, n-butylisobutyl 4-methyl-5-ethylphthalate, n-butylisobutyl 4-ethyl-5-methyl phthalate, n-butylisohexyl 3-methylphthalate, n-butyl isohexyl 4-methylphthalate, n-butylisohexyl 3-ethylphthalate, n-butylisohexyl 4-ethylphthalate, n-butylisohexyl 3-t-butyl phthalate, n-butylisohexyl 4-t-butylphthalate, n-butyl isohexyl 4,5-dimethylphthalate, n-butylisohexyl 4,5-diethyl phthalate, n-butylisohexyl 4-methyl-5-ethylphthalate, and n-butyl isohexyl 4-ethyl-5-methylphthalate.
Specific examples of the compounds of the above formula (1), wherein n=1 and R1 is an alkyl group with 1 to 5 carbon atoms, or n=2 and R1 is an alkyl group with 1 to 5 carbon atoms or a halogen atom, and one of the groups R2 and R3 is an alkyl group with 4 to 8 carbon atoms including a tertiary carbon atom include ethyl-t-butyl 3-methylphthalate, ethyl-t-butyl 4-methylphthalate, ethyl-t-butyl 3-ethylphthalate, ethyl-t-butyl 4-ethylphthalate, ethyl-t-butyl 4,5-dimethyl phthalate, ethyl-t-butyl 4,5-diethylphthalate, ethyl-t-butyl 4-methyl-5-ethylphthalate, ethyl-t-butyl 4-ethyl-5-methylphthalate, ethyl-t-butyl 4-methyl-5-chloro phthalate, ethyl-t-butyl 4-chloro-5-methylphthalate, ethyl-t-butyl 4-methyl-5-bromophthalate, ethyl-t-butyl 4-bromo-5-methylphthalate, ethyl-t-butyl 4-ethyl-5-chloro phthalate, ethyl-t-butyl 4-chloro-5-ethylphthalate, ethyl-t-butyl 4-ethyl-5-bromophthalate, ethyl-t-butyl 4-bromo-5-ethylphthalate, ethyl neopentyl 3-methylphthalate, ethylneopentyl 4-methylphthalate, ethylneopentyl 3-ethyl phthalate, ethylneopentyl 4-ethylphthalate, ethylneopentyl 4,5-dimethylphthalate, ethylneopentyl 4,5-diethylphthalate, ethylneopentyl 4-methyl-5-ethylphthalate, ethylneopentyl 4-ethyl-5-methylphthalate, ethylneopentyl 4-methyl-5-chlorophthalate, ethylneopentyl 4-chloro-5-methylphthalate, ethylneopentyl 4-methyl-5-bromophthalate, ethylneopentyl 4-bromo-5-methylphthalate, ethylneopentyl 4-ethyl-5-chloro phthalate, ethylneopentyl 4-chloro-5-ethylphthalate, ethyl neopentyl 4-ethyl-5-bromophthalate, ethylneopentyl 4-bromo-5-ethylphthalate, n-butylneopentyl 3-methylphthalate, n-butylneopentyl 4-methylphthalate, n-butylneopentyl 3-ethylphthalate, n-butylneopentyl 4-ethylphthalate, n-butylneopentyl 4,5-dimethylphthalate, n-butylneopentyl 4,5-diethylphthalate, n-butylneopentyl 4-methyl-5-ethyl phthalate, n-butylneopentyl 4-ethyl-5-methylphthalate, n-butylneopentyl 4-methyl-5-clilorophthalate, n-butyl neopentyl 4-chloro-5-methylphthalate, n-butylneopentyl 4-methyl-5-bromo phthalate, n-butylneopentyl 4-bromo-5-methylphthalate, n-butyl neopentyl 4-ethyl-5-chloro phthalate, n-butylneopentyl 4-chloro-5-ethylphthalate, n-butylneopentyl 4-ethyl-5-bromophthalate, and n-butyl neopentyl 4-bromo-5-ethylphthalate.
Specific examples of the compounds of the above formula (1), wherein n=1 or 2, R1 is an alkyl group with 6 to 8 carbon atoms, and both R2 and R3 are alkyl groups with 4 to 8 carbon atoms including a tertiary carbon atom include di-t-butyl 4-n-hexylphthalate, di-t-butyl 4-isohexylphthalate, di-t-butyl 4-(2,2-dimethylbutyl)phthalate, di-t-butyl 4-(2,2-dimethylpentyl)phthalate, di-t-butyl isooctyl phthalate, di-t-butyl 4-n-hexyl-5-chlorophthalate, di-t-butyl 4-n-hexyl-5-bromophthalate, di-t-butyl 4-isohexyl-5-chlorophthalate, di-t-butyl 4-isohexyl-5-bromophthalate, di-t-butyl 4-(2,2-dimethylbutyl)-5-chlorophthalate, di-t-butyl 4-(2,2-dimethylbutyl)-5-bromophthalate, di-t-butyl 4-(2,2-dimethyl pentyl) phthalate, di-t-butyl isooctylphthalate, dineopentyl 4-n-hexylphthalate, dineopentyl 4-isohexylphthalate, dineopentyl 4-(2,2-dimethylbutyl)phthalate, dineopentyl 4-(2,2-dimethylpentyl)phthalate, dineopentyl isooctyl phthalate, dineopentyl 4-n-hexyl-5-chlorophthalate, dineopentyl 4-n-hexyl-5-bromophthalate, dineopentyl 4-isohexyl-5-chlorophthalate, dineopentyl 4-isohexyl-5-bromophthalate, dineopentyl 4-(2,2-dimethylbutyl)-5-chlorophthalate, dineopentyl 4-(2,2-dimethylbutyl)-5-bromophthalate, dineopentyl 4-(2,2-dimethylpentyl) phthalate, and dineopentyl isooctylphthalate.
Of these, preferable compounds are diethyl 4-methyl phthalate, di-n-butyl 4-methylphthalate, diisobutyl 4-methyl phthalate, diisohexyl 4-methylphthalate, diisooctyl 4-methyl phthalate, diethyl 4-ethylphthalate, di-n-butyl 4-ethyl phthalate, diisobutyl 4-ethylphthalate, diisohexyl 4-ethyl phthalate, diisooctyl 4-ethylphthalate, diethyl 4-t-butyl phthalate, di-n-butyl 4-t-butylphthalate, diisobutyl 4-t-butyl phthalate, diisohexyl 4-t-butylphthalate, diisooctyl 4-t-butylphthalate, diethyl 4,5-dimethylphthalate, di-n-butyl 4,5-dimethylphthalate, diisohexyl 4,5-dimethyl phthalate, diisooctyl 4,5-dimethylphthalate, diethyl 4,5-diethylphthalate, di-n-butyl 4,5-diethylphthalate, diisohexyl 4,5-diethylphthalate, diisooctyl 4,5-diethyl phthalate, diethyl 4-methyl-5-chlorophthalate, diethyl 4-methyl-5-bromophthalate, diethyl 4-ethyl-5-chloro phthalate, diethyl 4-ethyl-5-bromophthalate, di-n-butyl 4-methyl-5-chlorophthalate, di-n-butyl 4-methyl-5-bromo phthalate, di-n-butyl 4-ethyl-5-chlorophthalate, di-n-butyl 4-ethyl-5-bromophthalate, diisobutyl 4-methyl-5-chlorophthalate, diisobutyl 4-methyl-5-chlorophthalate, diisobutyl 4-methyl-5-bromophthalate, diisobutyl 4-ethyl-5-chlorophthalate, diisobutyl 4-ethyl-5-bromophthalate, diisohexyl 4-methyl-5-chlorophthalate, diisohexyl 4-methyl-5-bromophthalate, diisohexyl 4-ethyl-5-chlorophthalate, diisohexyl 4-ethyl-5-bromophthalate, diisooctyl 4-methyl-5-chlorophthalate, diisooctyl 4-methyl-5-bromophthalate, diisooctyl 4-ethyl-5-chloro phthalate, diisooctyl 4-ethyl-5-bromophthalate, and the like.
Specific examples of the compounds of the above formula (1), wherein n=1 or 2, R1 is a halogen atom, and at least one of the groups R2 or R3 is an alkyl group with 1 to 12 carbon atoms other than the alkyl group with 4 to 8 carbon atoms including a tertiary carbon atom include diethyl 3-fluoro phthalate, diethyl 4-fluoro phthalate, diethyl 3-chloro phthalate, diethyl 4-chlorophthalate, diethyl 3-bromo phthalate, diethyl 4-bromophthalate, diethyl 3-iodophthalate, diethyl 4-iodophthalate, diethyl 4,5-dichloro phthalate, diethyl 4,5-dibromophthalate, diethyl 4-chloro-5-bromo phthalate, di-n-butyl 3-fluorophthalate, di-n-butyl 4-fluorophthalate, di-n-butyl 3-chlorophthalate, di-n-butyl 4-chlorophthalate, di-n-butyl 3-bromophthalate, di-n-butyl 4-bromophthalate, di-n-butyl 3-iodophthalate, di-n-butyl 4-iodophthalate, di-n-butyl 4,5-dichlorophthalate, di-n-butyl 4,5-dibromophthalate, di-n-butyl 4-chloro-5-bromo phthalate, diisobutyl 3-fluorophthalate, diisobutyl 4-fluorophthalate, diisobutyl 3-chlorophthalate, diisobutyl 4-chlorophthalate, diisobutyl 3-bromophthalate, diisobutyl 4-bromophthalate, diisobutyl 3-iodophthalate, diisobutyl 4-iodophthalate, diisobutyl 4,5-dichlorophthalate, diisobutyl 4,5-dibromophthalate, diisobutyl 4-chloro-5-bromophthalate, diisohexyl 3-fluorophthalate, diisohexyl 4-fluorophthalate, diisohexyl 3-chlorophthalate, diisohexyl 4-chlorophthalate, diisohexyl 3-bromophthalate, diisohexyl 4-bromophthalate, diisohexyl 3-iodophthalate, diisohexyl 4-iodophthalate, isohexyl 4,5-dichlorophthalate, diisohexyl 4,5-dibromophthalate, diisohexyl 4-chloro-5-bromophthalate, diisooctyl 3-fluorophthalate, diisooctyl 4-fluorophthalate, diisooctyl 3-chlorophthalate, diisooctyl 4-chlorophthalate, diisooctyl 3-bromophthalate, diisooctyl 4-bromophthalate, diisooctyl 3-iodophthalate, diisooctyl 4-iodophthalate, diisooctyl 4,5-dichlorophthalate, diisooctyl 4,5-dibromophthalate, diisooctyl 4-chloro-5-bromo phthalate, di-n-decyl 4-chlorophthalate, isodecyl 4-chloro phthalate, di-n-decyl 4-bromophthalate, isodecyl 4-bromo phthalate, ethyl-n-butyl 3-fluorophthalate, ethyl-n-butyl 4-fluorophthalate, ethyl-n-butyl 3-chlorophthalate, ethyl-n-butyl 4-chlorophthalate, ethyl-n-butyl 3-bromophthalate, ethyl-n-butyl 4-bromophthalate, ethyl-n-butyl 3-iodo phthalate, ethyl-n-butyl 4-iodophthalate, ethyl-n-butyl 4,5-dichlorophthalate, ethyl-n-butyl 4,5-dibromophthalate, ethyl-n-butyl 4-chloro-5-bromophthalate, ethylisobutyl 3-fluorophthalate, ethylisobutyl 4-fluorophthalate, ethylisobutyl 3-chlorophthalate, ethylisobutyl 4-chloro phthalate, ethylisobutyl 3-bromophthalate, ethylisobutyl 4-bromophthalate, ethylisobutyl 3-iodophthalate, ethyl isobutyl 4-iodophthalate, ethylisobutyl 4,5-dichloro phthalate, ethylisobutyl 4,5-dibromophthalate, ethyl isobutyl 4-chloro-5-bromophthalate, ethylisohexyl 3-fluorophthalate, ethylisohexyl 4-fluorophthalate, ethyl isohexyl 3-chlorophthalate, ethylisohexyl 4-chlorophthalate, ethylisohexyl 3-bromophthalate, ethylisohexyl 4-bromo phthalate, ethylisohexyl 3-iodophthalate, ethylisohexyl 4-iodophthalate, ethylisohexyl 4,5-dichlorophthalate, ethyl isohexyl 4,5-dibromophthalate, ethylisohexyl 4-chloro-5-bromophthalate, ethylisobutyl 3-fluorophthalate, ethyl isobutyl 4-fluorophthalate, ethylisobutyl 3-chlorophthalate, ethylisobutyl 4-chlorophthalate, ethylisobutyl 3-bromo phthalate, ethylisobutyl 4-bromophthalate, ethylisobutyl 3-iodophthalate, ethylisobutyl 4-iodophthalate, ethyl isobutyl 4,5-dichlorophthalate, ethylisobutyl 4,5-dibromo phthalate, ethylisobutyl 4-chloro-5-bromophthalate, n-butyl isobutyl 3-fluorophthalate, n-butylisobutyl 4-fluoro phthalate, n-butylisobutyl 3-chlorophthalate, n-butyl isobutyl 4-chlorophthalate, n-butyl isobutyl 3-bromophthalate, n-butylisobutyl 4-bromophthalate, n-butylisobutyl 3-iodo phthalate, n-butylisobutyl 4-iodophthalate, n-butylisobutyl 4,5-dichlorophthalate, n-butylisobutyl 4,5-dibromophthalate, n-butylisobutyl 4-chloro-5-bromophthalate, n-butylisohexyl 3-fluorophthalate, n-butylisohexyl 4-fluorophthalate, n-butylisohexyl 3-chlorophthalate, n-butylisohexyl 4-chlorophthalate, n-butylisohexyl 3-bromophthalate, n-butyl isohexyl 4-bromophthalate, n-butylisohexyl 3-iodophthalate, n-butylisohexyl 4-iodophthalate, n-butylisohexyl 4,5-dichlorophthalate, n-butylisohexyl 4,5-dibromophthalate, n-butylisohexyl 4-chloro-5-bromophthalate, ethyl-t-butyl 3-fluorophthalate, ethyl-t-butyl 4-fluorophthalate, ethyl-t-butyl 3-chlorophthalate, ethyl-t-butyl 4-chloro phthalate, ethyl-t-butyl 3-bromophthalate, ethyl-t-butyl 4-bromophthalate, ethyl-t-butyl 3-iodophthalate, ethyl-t-butyl 4-iodophthalate, ethyl-t-butyl 4,5-dichlorophthalate, ethyl-t-butyl 4,5-dibromophthalate, ethyl-t-butyl 4-chloro-5-bromophthalate, ethylneopentyl 3-fluorophthalate, ethyl neopentyl 4-fluorophthalate, ethylneopentyl 3-chloro phthalate, ethyl neopentyl 4-chlorophthalate, ethylneopentyl 3-bromophthalate, ethylneopentyl 4-bromophthalate, ethyl neopentyl 3-iodophthalate, ethylneopentyl 4-iodophthalate, ethylneopentyl 4,5-dichloro phthalate, ethylneopentyl 4,5-dibromophthalate, ethylneopentyl 4-chloro-5-bromo phthalate, n-butyl-t-butyl 3-fluorophthalate, n-butyl-t-butyl 4-fluorophthalate, n-butyl-t-butyl 3-chlorophthalate, n-butyl-t-butyl 4-chlorophthalate, n-butyl-t-butyl 3-bromo phthalate, n-butyl-t-butyl 4-bromophthalate, n-butyl-t-butyl 3-iodophthalate, n-butyl-t-butyl 4-iodophthalate, n-butyl-t-butyl 4,5-dichlorophthalate, n-butyl-t-butyl 4,5-dibromo phthalate, n-butyl-t-butyl 4-chloro-5-bromophthalate, n-butylneopentyl 3-fluorophthalate, n-butylneopentyl 4-fluorophthalate, n-butylneopentyl 3-chlorophthalate, n-butylneopentyl 4-chlorophthalate, n-butylneopentyl 3-bromophthalate, n-butylneopentyl 4-bromophthalate, n-butyl neopentyl 3-iodophthalate, n-butylneopentyl 4-iodophthalate, n-butylneopentyl 4,5-dichlorophthalate, n-butylneopentyl 4,5-dibromophthalate, and n-butylneopentyl 4-chloro-5-bromo phthalate.
Of these, preferable compounds are diethyl 4-bromo phthalate, di-n-butyl 4-bromophthalate, diisobutyl 4-bromo phthalate, diethyl 4-chlorophthalate, di-n-butyl 4-chloro phthalate, diisobutyl 4-chlorophthalate, diisohexyl 4-chloro phthalate, diisooctyl 4-chlorophthalate, diisohexyl 4-bromo phthalate, diisooctyl 4-bromophthalate, diethyl 4,5-dichloro phthalate, di-n-butyl 4,5-dichlorophthalate, isohexyl 4,5-dichlorophthalate, and diisooctyl 4,5-dichlorophthalate.
Among the above-described phthalic acid diester derivatives, particularly preferred compounds as an electron donor which is one of the components of the catalyst for the olefin polymerization are dineopentyl 4-methylphthalate, dineopentyl 3-fluorophthalate, dineopentyl 4,5-dimethyl phthalate, dineopentyl 4-bromophthalate, t-butylneopentyl phthalate, di-n-butyl 4-methylphthalate, di-n-butyl 4-t-butyl phthalate, diethyl 4-methylphthalate, diethyl 4-t-butyl phthalate, di-n-butyl 4-bromophthalate, di-n-butyl 4-chloro phthalate, di-n-butyl 4,5-dichlorophthalate, diisohexyl 4-bromophthalate, and dineopentyl 4-t-butylphthalate. These phthalic acid diesters derivatives may be used either individually or in combinations of two or more.
The phthalic acid diester derivatives of the present invention are useful as an electron donor of various olefin polymerization catalysts. Specifically, these phthalic acid diesters and their derivatives are useful as an electron donor of catalysts in the homo- or copolymerization of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinyl cyclohexane, and the like, preferably in the homopolymerization of ethylene or propylene, or copolymerization of ethylene and propylene. In particular, these compounds are ideal as electron donors of catalysts used in the homopolymerization of propylene or the copolymerization of ethylene and propylene.
The phthalic acid diester derivatives of the present invention can be prepared by various methods. A most simple method is reacting a commercially available phthalate with an alkyl halide, followed by hydrolysis of the resulting product. A number of synthetic methods of esters are known as described, for example, in xe2x80x9cLecture of Experimental Chemistryxe2x80x9d (the fourth edition, vol. 22). Some examples are described here. A most common ester synthetic method comprises an application of the dehydration reaction of a carboxylic acid and alcohol. A mineral acid such as hydrochloric acid and sulfuric acid or a base such as triethylamine may be used as a catalyst. Another well-known method comprises use of a dehydrating agent for the synthesis of esters. For example, dicyclohexyl carbodiimide, trifluoroacetic acid anhydride, and the like are used as the dehydrating agent. A synthetic method using a carboxylic acid anhydride instead of carboxylic acid is also known. Moreover, a method of synthesizing an ester from an acid halide is known. This method is commonly used for the esterification of a carboxylic acid with a low reactivity due to steric hindrance, for example. For synthesis of a carboxylic acid ester of a dibasic acid, a method of preparing an intermediate such as a mono-ester or half-ester, then obtaining a diester by directly esterifying this intermediate or via an acid halide is known. These methods and other known methods may be used.
In a specific synthesis method of dineopentyl 4-methyl phthalate, 4-methylphthalic acid and neopentyl alcohol are charged into a flask and refluxed for 2 hours in the presence of sulfuric acid. After completion of the reaction, the reaction mixture is allowed to cool to the room temperature, and distilled water and ether are added to the mixture to extract the reaction product into the ether layer. After repetition of a washing procedure of the ether layer by flushing, an aqueous solution of sodium hydrogen carbonate is added, followed by neutralization of the water layer. A salt solution is added and the washing procedure using distilled water is repeated. Sodium sulfate is then added to the ether layer, followed by filtration. Ether contained in the resulting filtrate is removed by vacuum distillation. Vacuum distillation is repeated to obtain a yellow liquid. The liquid is cooled and recrystallized from ethanol to obtain white crystals.
The phthalic acid diester derivative thus obtained can be identified by the nuclear magnetic resonance spectroscopy (1H-NMR), Raman spectrometry, mass spectrometry (MS), and the like.
The use of the phthalic acid diester derivatives of the present invention as an electron donor of an olefin polymerization catalyst remarkably improves the polymerization activity, the yield of high stereoregularity polymers, and the response to hydrogen of the catalyst as compared with conventionally known high performance catalyst.